A series of heterofluorene polymers, containing electron-deficient heteroatoms, were designed for investigation. Indium was first chosen for heteroatom substitution, due to the known Lewis acidity of Group-13 elements, and supermesityl (2,4,6-tri-tert-butylphenyl) was used as a protective substituent to reduce unwanted hydrolysis of indafluorene by sterically protecting the vacant p-orbitals of the indium heteroatom. An indafluorene small molecule was synthesized as a model system; however, 1H NMR analysis showed the compound demonstrated poor stability when exposed to air, so an indafluorene polymer based on this design was not pursued. A novel borafluorene was investigated, featuring an OCO pincer-type ligand as the protective substituent, which stabilizes the boron heteroatom through weak B-O dative bonds. A borafluorene small molecule (BMMP-BF) was synthesized as a model system, and demonstrated robust stability under ambient conditions. Surprisingly, BMMP-BF also exhibited an extraordinarily large Stokes shift, and the cause behind this intriguing optical behavior was investigated. The borafluorene was then functionalized as a monomer and incorporated into two copolymer systems in order to examine the effects that extended conjugation and comonomer electron affinity would have on the optoelectronic properties. Optical characterization showed that both copolymers had a change in their optical behavior, relative to BMMP-BF, as demonstrated by smaller Stokes shifts, and CV analysis revealed that both copolymers possessed low lying LUMOs and narrow optical bandgaps. It is our hope that this research will lead to the development of novel n-type semiconductors. A novel carbazole-based polymer was explored, featuring a cationic ammonium functional group incorporated in the conjugated polymer backbone. A quaternized carbazolium small molecule was synthesized through an intramolecular cyclization mechanism, and served as a model system. The small molecule was characterized by NMR and XRD, and exchange of the counter ion was effectively demonstrated. We intended to synthesize a carbazole polymer and characterize the polymer in a non-ionic state, then quaternize the monomer sub-units during a post-polymerization phase to achieve a carbazolium polyelectrolyte. However, the non-ionic polymer had poor solubility in common organic solvents, which restricted access to the desired polyelectrolyte, and several efforts to form a soluble polymer were ultimately unsuccessful.